Pesticidally activi mixtures comprising anthranilamide compounds

ABSTRACT

and at least one further pesticidal active ingredient. The pesticidal mixtures are useful for combating and controlling insects, acarids or nematodes in and on plants, and for protecting such plants being infested with pests.

The present invention relates to mixtures of active ingredients having synergistically enhanced action and to methods comprising applying said mixtures.

The present invention relates to pesticidal mixtures comprising as active compounds

-   -   1) at least one anthranilamide compound of formula (I):

-   -   wherein     -   X is N, CF, CCl, CBr or Cl;     -   R¹ is H, F, Cl, Br or CN;     -   R² is CH₃, Cl, Br or F;     -   R³ is F, Cl, Br, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or Q;     -   R⁴ is N═S(O)_(k)R⁵R⁶ or NR⁷R⁸;     -   R⁵, R⁶ are independently of one another hydrogen, C₁-C₄-alkyl,         C₃-C₈-cycloalkyl, or         -   R⁵ and R⁶ together represent a C₂-C₇-alkylene,             C₂-C₇-alkenylene or C₆-C₉-alkynylene chain forming together             with the sulfur atom to which they are attached a 3-, 4-,             5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially             unsaturated or fully unsaturated ring,     -   k is 0 or 1;     -   R⁷ and R⁸ are independently of one another hydrogen,         C₁-C₆-alkyl, C₃-C₆-cycloalkyl, cyclopropylmethyl,         cyclopropylethyl;     -   R⁹, R¹⁰ are independently of one another H, F, Cl, Br; and     -   Q is a —CH₂-tetrazole radical;     -   or a stereoisomer, salt, crystalline form or N-oxide thereof;     -   and     -   2) one or more pesticidally active compounds II selected from         the group of     -   2.1. a compound of formula II.1

-   -   2.2. a compound of formula II.2

(II.2)

R^(II.2.1a) R^(II.2.1b) II.2-1 H CH₃ II.2-2 H Cl II.2-3 CH₃ Cl II.2-4 CH₃ CH₃ II.2-5 O—CH₂CH₃ CH₃ II.2-6 O—CH₃ CH₃ II.2-7 O—CH₃ Cl II.2-8 O—CH₂CH₃ Cl

-   -   2.3. a compound of formula II.3-1 or II.3-2

-   -   2.4. a compound of formula II.4-1 or II-4.2

-   -   2.5. a compound of formula II.5

-   -   -   wherein the moiety —C(O)NHR^(II.5) in compounds II.5-1 to             II.5-4 is connected to position 4 of the indazole moiety and             the moiety —C(O)NHR^(II.5) in compounds II.5-5 to II.5-10 is             connected to position 5 of the indazole moiety;

    -   2.6. a compound of formula II.6

in a synergistically effective amount.

The asterisk “*” denotes the bond in the group, which forms the connection to the rest of the molecule.

One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.

Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.

There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.

Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests which have developed natural or adapted resistance against the active compound in question.

Therefore there is a need for pest control agents that help prevent or overcome resistance induced by pesticides.

Furthermore, there is a desire for pesticide compounds or combination of compounds, which when applied improve plants, which may result in “plant health”, “vitality of plant propagation material” or “increased plant yield”.

It is therefore an object of the present invention to provide agricultural combinations which solves one or more than one of the discussed problems as

-   -   reducing the dosage rate,     -   enhancing the spectrum of activity,     -   combining knock-down activity with prolonged control,     -   improving resistance management,     -   Improved plant health;     -   Improved vitality of plant propagation material, also termed         seed vitality;     -   Increased plant yield.

It was therefore an object of the present invention to provide pesticidal mixtures which solve at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining knock-down activity with prolonged control or as to resistance management.

It has been found that this object is in part or in whole achieved by the combination of active compounds as defined herein.

As used herein, the term “mixture(s) of the present invention” or “mixture(s) according to the invention” refers to the mixtures comprising compound(s) of formula (I) as defined above, which are also referred to as “compound(s) of formula I” or “compound(s) I” or “formula I compound(s)”, and compound(s) of formula (II) as defined above, i.e. compounds of formula “II.1”, (II.2), (II.3.), (II.4), (II.5) or (II.6), which are also referred to as “compound(s) of formula II” or “compound(s) II”.

The compounds of formula I and the compounds II are understood to include their salts, tautomers, stereoisomers, and N-oxides.

The present invention relates to a mixture of at least one compound I of the present invention with at least one mixing partner II as defined above. In one embodiment, the invention relates to binary mixtures of one compound I with one mixing partner II as defined above as component II.

Preferred weight ratios for such binary mixtures are from 5000:1 to 1:5000, preferably from 1000:1 to 1:1000, more preferably from 100:1 to 1:100, particularly preferably from 10:1 to 1:10.

In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.

In the mixtures of the present invention, the ingredients may be used sequentially or in combination with each other, if appropriate also added only immediately prior to use (tank mix).

For example, the plant(s) may be sprayed with compound II either before or after being treated with compound I.

Depending on the substitution pattern, the compounds of the present invention may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or pure diastereomers of the compounds of the present invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds of the present invention or their mixtures. Suitable compounds of the formula of the present invention also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group. The term “stereoisomer(s)” encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).

Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.

In general, suitable “agriculturally useful salts” or “agriculturally acceptable salts” are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH₄ ⁺) and substituted ammonium in which one to four of the hydrogen atoms are replaced by C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae (I) or (II) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

Preferred compounds of the present invention are compounds of formula (I) or (II) or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally or veterinarily acceptable salt.

The compounds of the present invention may be present in the form of their N-oxides. The term “N-oxide” includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides of compounds of the present invention can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions compounds of the present invention, i.e. of the formula (I) or (II), may form N-oxides.

The compounds I of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of formula (I), their enantiomers or diastereomers, mixtures of different crystalline states of the respective compound of formula (I), its enantiomers or diastereomers, as well as amorphous or crystalline salts thereof.

The term “co-crystal” denotes a complex of the compounds of the present invention or a stereoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules (preferably one molecule type), wherein usually the ratio of the compound according to the invention and the other molecule is a stoichiometric ratio.

The term “solvate” denotes a co-complex of the compounds of the present invention, or a stereoisomer, salt, tautomer or N-oxide thereof, with solvent molecules. The solvent is usually liquid.

Examples of solvents are methanol, ethanol, toluol, xylol. A preferred solvent which forms solvates is water, which solvates are referred to as “hydrates”. A solvate or hydrate is usually characterized by the presence of a fixed number of n molecules solvent per m molecules compound according to the invention.

The organic moieties mentioned in the above definitions of the variables are—like the term halogen—collective terms for individual listings of the individual group members. The prefix C_(n)-C_(m) indicates in each case the possible number of carbon atoms in the group.

The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.

The term “partially or fully halogenated” will be taken to mean that 1 or more, e.g. 1, 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine. A partially or fully halogenated radical is termed below also “halo-radical”. For example, partially or fully halogenated alkyl is also termed haloalkyl.

The term “alkyl” as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 12 or 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of C₁-C₄-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl. Examples for C₁-C₆-alkyl are, apart those mentioned for C₁-C₄-alkyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. Examples for C₁-C₁₀-alkyl are, apart those mentioned for C₁-C₆-alkyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.

The term “alkylene” (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term “haloalkyl” as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms (“C₁-C₁₀-haloalkyl”), frequently from 1 to 6 carbon atoms (“C₁-C₆-haloalkyl”), more frequently 1 to 4 carbon atoms (“C₁-C₁₀-haloalkyl”), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from C₁-C₄-haloalkyl, more preferably from C₁-C₂-haloalkyl, more preferably from halomethyl, in particular from C₁-C₂-fluoroalkyl. Halomethyl is methyl in which 1, 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like. Examples for C₁-C₂-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. Examples for C₁-C₂-haloalkyl are, apart those mentioned for C₁-C₂-fluoroalkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 2-chloroethyl, 2,2,-dichloroethyl, 2,2,2-trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 1-bromoethyl, and the like. Examples for C₁-C₄-haloalkyl are, apart those mentioned for C₁-C₂-haloalkyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1,1,1-trifluoroprop-2-yl, 3-chloropropyl, 4-chlorobutyl and the like.

The term “cycloalkyl” as used herein (and in the cycloalkyl moieties of other groups comprising a cycloalkyl group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms (“C₃-C₁₀-cycloalkyl”), preferably 3 to 8 carbon atoms (“C₃-C₈-cycloalkyl”) or in particular 3 to 6 carbon atoms (“C₃-C₆-cycloalkyl”). Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.

The term “cycloalkyl-alkyl” used herein denotes a cycloalkyl group, as defined above, which is bound to the remainder of the molecule via an alkylene group. The term “C₃-C₈-cycloalkyl-C₁-C₄-alkyl” refers to a C₃-C₈-cycloalkyl group as defined above which is bound to the remainder of the molecule via a C₁-C₄-alkyl group, as defined above. Examples are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, and the like.

The term “alkenyl” as used herein denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 10 (“C₂-C₁₀-alkenyl”), preferably 2 to 6 carbon atoms (“C₂-C₆-alkenyl”), in particular 2 to 4 carbon atoms (“C₂-C₄-alkenyl”), and a double bond in any position, for example C₂-C₄-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl or 2-methyl-2-propenyl; C₂-C₆-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl and the like, or C₂-C₁₀-alkenyl, such as the radicals mentioned for C₂-C₆-alkenyl and additionally 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and the positional isomers thereof.

The term “alkenylene” (or alkenediyl) as used herein in each case denotes an alkenyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term “alkynyl” as used herein denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 10 (“C₂-C₁₀-alkynyl”), frequently 2 to 6 (“C₂-C₆-alkynyl”), preferably 2 to 4 carbon atoms (“C₂-C₄-alkynyl”) and one or two triple bonds in any position, for example C₂-C₄-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl and the like, C₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and the like.

The term “alkynylene” (or alkynediyl) as used herein in each case denotes an alkynyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term “alkoxy” as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 10 carbon atoms (“C₁-C₁₀-alkoxy”), frequently from 1 to 6 carbon atoms (“C₁-C₆-alkoxy”), preferably 1 to 4 carbon atoms (“C₁-C₄-alkoxy”), which is bound to the remainder of the molecule via an oxygen atom. C₁-C₂-Alkoxy is methoxy or ethoxy. C₁-C₄-Alkoxy is additionally, for example, n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1,1-dimethylethoxy (tert-butoxy). C₁-C₆-Alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy. C₁-C₈-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof. C₁-C₁₀-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof.

The term “haloalkoxy” as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 10 carbon atoms (“C₁-C₁₀-haloalkoxy”), frequently from 1 to 6 carbon atoms (“C₁-C₆-haloalkoxy”), preferably 1 to 4 carbon atoms (“C₁-C₄-haloalkoxy”), more preferably 1 to 3 carbon atoms (“C₁-C₃-haloalkoxy”), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. C₁-C₂-Haloalkoxy is, for example, OCH₂F, OCHF₂, OCF₃, OCH₂Cl, OCHCl₂, OCCl₃, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC₂F_(5.) C₁-C₄-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH₂—C₂F₅, OCF₂—C₂F₅, 1-(CH₂F)-2-fluoroethoxy, 1-(CH₂Cl)-2-chloroethoxy, 1-(CH₂Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. C₁-C₆-Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.

A saturated, partially unsaturated or unsaturated 3- to 10-membered ring is e.g. a 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, is a ring system wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system e.g. thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazole, benzo[b]thiophene, benzo[b]furan, indole, benzo[c]thiophene, benzo[c]furan, isoindole, benzoxazole, benzthiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benztriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine, 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxazolidine or thiazolidine, oxirane or oxetane.

A saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur also is e.g.

a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, such as pyridine, pyrimidine, (1,2,4)-oxadiazole, (1,3,4)-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine; or

a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 nitrogen atom and 0 to 2 further heteroatoms selected from oxygen, nitrogen and sulfur, preferably from oxygen and nitrogen, such as piperidine, piperazin and morpholine.

Preferably, this ring system is a saturated, partially unsaturated or unsaturated 3- to 6-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system.

Most preferably, this ring system is a radical of pyridine, pyrimidine, (1,2,4)-oxadiazole, 1,3,4-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane or oxetane.

Compounds I

The anthranilamide compounds of formula (I) can be prepared as described in the literature, e.g. as described in WO2001/070671, WO2003/015519, WO2004/067528, WO2005/077934, WO2007/006670, WO2007/144100 or WO2010/069502; or by analogous methods; or they are commercially available.

The preparation of the compounds of formula I above may lead to them being obtained as isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.

Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.

Compounds II

The compounds of formula (II) can be prepared as described in the literature.

The compound of formula II.1 (IUPAC name: N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide) is known from EP2910126. The compounds of formula II.2 are known from WO2014/191271 and WO2014/187847. The compounds of formula II.3, respectively II.3-1 (IUPAC name: 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine) and II.3-2 (IUPAC name: 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine) are known from WO2015/059039 and WO2015/190316. The compound of formula II.4-1 (IUPAC name: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide) and II-4-2 (IUPAC name: 4-[5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide) are known from WO2013/050302. The compounds of formula II.4-1 and II.4-2, in which the cycloserine has R-configuration but the isoxazoline moiety may vary, are present as pure stereoisomers or as mixtures thereof:

Preferred are II.4-1S and II.4-2S.

The compounds of formula II.5 are known from WO2015/038503.

The compounds of formula II.6 are known from US2014/0213448.

Preferences

In one embodiment, the invention relates to mixtures wherein in the anthranilamide compound I

X is N;

R⁹ is Cl and R¹⁰ is H;

and the remaining substituents are as defined above.

In one embodiment, the invention relates to mixtures wherein in the anthranilamide compound I

X is N,

R⁹ is Cl and R¹⁰ is H;

R¹ is H, F, Cl, Br or CN;

R² is CH₃, Cl, Br or F;

R³ is F, Cl, Br, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or Q;

R⁴ is N═S(O)_(k)R⁵R⁶ or NR⁷R⁸;

R⁵, R⁶ are independently of one another hydrogen, C₁-C₄-alkyl, C₃-C₈-cycloalkyl;

k is 0 or 1;

R⁷ and R⁸ are independently of one another hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, cyclopropylmethyl, cyclopropylethyl;

Q is a —CH₂-tetrazole radical;

or a stereoisomer, salt, crystalline form or N-oxide thereof.

In one embodiment, the invention relates to mixtures wherein in the anthranilamide compound I

X is N,

R⁹ is Cl and R¹⁰ is H;

R¹ is H, F, Cl, Br or CN;

R² is CH₃, Cl, Br or F;

R³ is F, Cl, Br, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or Q;

R⁴ is N═S(O)_(k)R⁵R⁶ or NR⁷R⁸;

R⁵, R⁶ are independently of one another C₁-C₄-alkyl, C₃-C₈-cycloalkyl;

k is 0 or 1;

R⁷ is hydrogen, and R⁸ is C₁-C₆-alkyl, C₃-C₆-cycloalkyl, cyclopropylmethyl, cyclopropylethyl;

Q is a —CH₂-tetrazole radical;

or a stereoisomer, salt, crystalline form or N-oxide thereof.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein in the anthranilamide compound I

X is N,

R⁹ is Cl and R¹⁰ is H;

R¹ is H, F, Cl, Br or CN;

R² is CH₃, Cl, Br or F;

R³ is F, Cl, Br, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or Q;

R⁴ is N═S(O)_(k)R⁵R⁶ or NR⁷R⁸;

R⁵, R⁶ are independently of one another C₁-C₄-alkyl, C₃-C₈-cycloalkyl;

k is 0 or 1;

R⁷ is hydrogen, and R⁸ is C₁-C₆-alkyl, C₃-C₆-cycloalkyl, cyclopropylmethyl, cyclopropylethyl;

Q is a —CH₂-tetrazole radical;

or a stereoisomer, salt, crystalline form or N-oxide thereof;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein in the anthranilamide compound I

X is N,

R⁹ is Cl and R¹⁰ is H;

R¹ is H, F, Cl, Br or CN;

R² is CH₃, Cl, Br or F;

R³ is Br or C₁-C₄-haloalkyl;

R⁴ is N═S(O)_(k)R⁵R⁶ or NR⁷R⁸;

R⁵, R⁶ are independently of one another C₁-C₄-alkyl;

k is 0 or 1;

R⁷ is H, and R⁸ is cyclopropylmethyl or cyclopropylethyl;

or a stereoisomer, salt, crystalline form or N-oxide thereof;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.1.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-1. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-2. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-3. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-4. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-5. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-6. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-7. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.2-8.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.3-1.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.3-2.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.4-1. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.4-2. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.4-1S. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.4-1R. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.4-2S. In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.4-2R.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.5-1, II.5-2, II.5-3, II.5-4, II.5-5, II.5-6, II.5-7, II.5-8, II.5-9, II.5-10, II.6-1, II.6-2, II.6-3 or II.6-4.

In one embodiment, the invention relates to mixtures wherein the compound II is the compound II.5-1, II.5-2, II.5-3 or II.5-4 (connected to position 4 of the indazole moiety). In another embodiment, the invention relates to mixtures wherein the compound II is the compound II.5-5, II.5-6, II.5-7, II.5-8, II.5-9 or II.5-10, (connected to position 5 of the indazole moiety).

In one embodiment, the invention relates to mixtures wherein, when the compound I is I.4 or I.5, the compound II is not the compound II.6-1 or II.6-2.

In one embodiment, the invention relates to mixtures wherein, when the compound I is I.2, I.4 or I.5, the compound II is not the compound II.6-1 or II.6-2.

In one embodiment (E1), the invention relates to mixtures, wherein in the anthranilamide compound I

-   -   X is N;     -   R¹ is Ck;     -   R² is CH₃ or Cl;     -   R³ is CF₃ or CHF₂;     -   R⁴ is N═S(O)_(k)R⁵R⁶;     -   R⁵, R⁶ are independently of one another hydrogen, C₁-C₄-alkyl,         C₃-C₈-cycloalkyl, or         -   R⁵ and R⁶ together represent a C₂-C₇-alkylene,             C₂-C₇-alkenylene or C₆-C₉-alkynylene chain forming together             with the sulfur atom to which they are attached a 3-, 4-,             5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially             unsaturated or fully unsaturated ring,     -   k is 0 or 1;     -   R⁹ is Cl and R¹⁰ is H.

In one embodiment, the invention relates to mixtures, wherein the anthranilamide compound I is a compound of formula I.1

wherein

-   -   R² is CH₃ or Cl;     -   R³ is CF₃ or CHF₂;     -   R⁵, R⁶ are independently of one another hydrogen, C₁-C₄-alkyl,         C₃-C₈-cycloalkyl,     -   k is 0 or 1;

The compounds of formula (I.1) are known from WO2007/006670, and they can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2013/024007, WO2013/024008, WO2013/076092, WO2014/154807, WO2014/202599, WO2014/184343 and/or WO2015/162260. Polymorphic forms of compounds of formula (I.1) are e.g. described in WO2013/024008 or WO2015/169883.

WO2014/053404 and WO2014/053405 describe pesticidal mixtures of the compounds of formula (I.1). However, they do not disclose the mixtures of the compounds of formula (I.1) with the compounds II according to the present invention, which show unexpected and synergistic effects in combination with each other.

In one embodiment, the invention relates to mixtures wherein the anthranilamide compound I is a compound of formula I.1 as described herein;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures, in which the anthranilamide compound I is a compound of formula I.1 as in Table 1.

TABLE 1 R² R³ R⁵ R⁶ k I.1-1 Me CF₃ C₂H₅ C₂H₅ 0 I.1-2 Cl CF₃ C₂H₅ C₂H₅ 0 I.1-3 Me CF₃ CH₃ CH₃ 0 I.1-4 Cl CF₃ CH₃ CH₃ 0 I.1-5 Me CF₃ CH(CH₃)₂ CH(CH₃)₂ 0 I.1-6 Cl CF₃ CH(CH₃)₂ CH(CH₃)₂ 0 I.1-7 Me CHF₂ C₂H₅ C₂H₅ 0 I.1-8 Cl CHF₂ C₂H₅ C₂H₅ 0 I.1-9 Me CHF₂ CH₃ CH₃ 0 I.1-10 Cl CHF₂ CH₃ CH₃ 0 I.1-11 Me CHF₂ CH(CH₃)₂ CH(CH₃)₂ 0 I.1-12 Cl CHF₂ CH(CH₃)₂ CH(CH₃)₂ 0 I.1-13 Me CF₃ C₂H₅ C₂H₅ 1 I.1-14 Cl CF₃ C₂H₅ C₂H₅ 1 I.1-15 Me CF₃ CH₃ CH₃ 1 I.1-16 Cl CF₃ CH₃ CH₃ 1 I.1-17 Me CF₃ CH(CH₃)₂ CH(CH₃)₂ 1 I.1-18 Cl CF₃ CH(CH₃)₂ CH(CH₃)₂ 1 I.1-19 Me CHF₂ C₂H₅ C₂H₅ 1 I.1-20 Cl CHF₂ C₂H₅ C₂H₅ 1 I.1-21 Me CHF₂ CH₃ CH₃ 1 I.1-22 Cl CHF₂ CH₃ CH₃ 1 I.1-23 Me CHF₂ CH(CH₃)₂ CH(CH₃)₂ 1 I.1-24 Cl CHF₂ CH(CH₃)₂ CH(CH₃)₂ 1

Preferred are mixtures, wherein the compound I is the compound I.1-1.

Preferred are mixtures, wherein the compound I is the compound I.1-3.

Preferred are mixtures, wherein the compound I is the compound I.1-5.

Preferred are mixtures, wherein the compound I is the compound I.1-7.

Preferred are mixtures, wherein the compound I is the compound I.1-11.

Thus, the invention relates to mixtures as shown in Table M1.

TABLE M1 Mixture Compound I Compound II M1.1 I.1-1 II.1 M1.2 I.1-1 II.2-1 M1.3 I.1-1 II.2-2 M1.4 I.1-1 II.2-3 M1.5 I.1-1 II.2-4 M1.6 I.1-1 II.2-5 M1.7 I.1-1 II.2-6 M1.8 I.1-1 II.2-7 M1.9 I.1-1 II.2-8 M1.10 I.1-1 II.3-1 M1.11 I.1-1 II.3-2 M1.12 I.1-1 II.4-1 M1.13 I.1-1 II.4-2 M1.14 I.1-1 II.4-1S M1.15 I.1-1 II.4-2S M1.16 I.1-1 II.4-1R M1.17 I.1-1 II.4-2R M1.18 I.1-1 II.5-1 M1.19 I.1-1 II.5-2 M1.20 I.1-1 II.5-3 M1.21 I.1-1 II.5-4 M1.22 I.1-1 II.5-5 M1.23 I.1-1 II.5-6 M1.24 I.1-1 II.5-7 M1.25 I.1-1 II.5-8 M1.26 I.1-1 II.5-9 M1.27 I.1-1 II.5-10 M1.28 I.1-1 II.6-1 M1.29 I.1-1 II.6-2 M1.30 I.1-1 II.6-3 M1.31 I.1-1 II.6-4 M1.32 I.1-2 II.1 M1.33 I.1-2 II.2-1 M1.34 I.1-2 II.2-2 M1.35 I.1-2 II.2-3 M1.36 I.1-2 II.2-4 M1.37 I.1-2 II.2-5 M1.38 I.1-2 II.2-6 M1.39 I.1-2 II.2-7 M1.40 I.1-2 II.2-8 M1.41 I.1-2 II.3-1 M1.42 I.1-2 II.3-2 M1.43 I.1-2 II.4-1 M1.44 I.1-2 II.4-2 M1.45 I.1-2 II.4-1S M1.46 I.1-2 II.4-2S M1.47 I.1-2 II.4-1R M1.48 I.1-2 II.4-2R M1.49 I.1-2 II.5-1 M1.50 I.1-2 II.5-2 M1.51 I.1-2 II.5-3 M1.52 I.1-2 II.5-4 M1.53 I.1-2 II.5-5 M1.54 I.1-2 II.5-6 M1.55 I.1-2 II.5-7 M1.56 I.1-2 II.5-8 M1.57 I.1-2 II.5-9 M1.58 I.1-2 II.5-10 M1.59 I.1-2 II.6-1 M1.60 I.1-2 II.6-2 M1.61 I.1-2 II.6-3 M1.62 I.1-2 II.6-4 M1.63 I.1-3 II.1 M1.64 I.1-3 II.2-1 M1.65 I.1-3 II.2-2 M1.66 I.1-3 II.2-3 M1.67 I.1-3 II.2-4 M1.68 I.1-3 II.2-5 M1.69 I.1-3 II.2-6 M1.70 I.1-3 II.2-7 M1.71 I.1-3 II.2-8 M1.72 I.1-3 II.3-1 M1.73 I.1-3 II.3-2 M1.74 I.1-3 II.4-1 M1.75 I.1-3 II.4-2 M1.76 I.1-3 II.4-1S M1.77 I.1-3 II.4-2S M1.78 I.1-3 II.4-1R M1.79 I.1-3 II.4-2R M1.80 I.1-3 II.5-1 M1.81 I.1-3 II.5-2 M1.82 I.1-3 II.5-3 M1.83 I.1-3 II.5-4 M1.84 I.1-3 II.5-5 M1.85 I.1-3 II.5-6 M1.86 I.1-3 II.5-7 M1.87 I.1-3 II.5-8 M1.88 I.1-3 II.5-9 M1.89 I.1-3 II.5-10 M1.90 I.1-3 II.6-1 M1.91 I.1-3 II.6-2 M1.92 I.1-3 II.6-3 M1.93 I.1-3 II.6-4 M1.94 I.1-4 II.1 M1.95 I.1-4 II.2-1 M1.96 I.1-4 II.2-2 M1.97 I.1-4 II.2-3 M1.98 I.1-4 II.2-4 M1.99 I.1-4 II.2-5 M1.100 I.1-4 II.2-6 M1.101 I.1-4 II.2-7 M1.102 I.1-4 II.2-8 M1.103 I.1-4 II.3-1 M1.104 I.1-4 II.3-2 M1.105 I.1-4 II.4-1 M1.106 I.1-4 II.4-2 M1.107 I.1-4 II.4-1S M1.108 I.1-4 II.4-2S M1.109 I.1-4 II.4-1R M1.110 I.1-4 II.4-2R M1.111 I.1-4 II.5-1 M1.112 I.1-4 II.5-2 M1.113 I.1-4 II.5-3 M1.114 I.1-4 II.5-4 M1.115 I.1-4 II.5-5 M1.116 I.1-4 II.5-6 M1.117 I.1-4 II.5-7 M1.118 I.1-4 II.5-8 M1.119 I.1-4 II.5-9 M1.120 I.1-4 II.5-10 M1.121 I.1-4 II.6-1 M1.122 I.1-4 II.6-2 M1.123 I.1-4 II.6-3 M1.124 I.1-4 II.6-4 M1.125 I.1-5 II.1 M1.126 I.1-5 II.2-1 M1.127 I.1-5 II.2-2 M1.128 I.1-5 II.2-3 M1.129 I.1-5 II.2-4 M1.130 I.1-5 II.2-5 M1.131 I.1-5 II.2-6 M1.132 I.1-5 II.2-7 M1.133 I.1-5 II.2-8 M1.134 I.1-5 II.3-1 M1.135 I.1-5 II.3-2 M1.136 I.1-5 II.4-1 M1.137 I.1-5 II.4-2 M1.138 I.1-5 II.4-1S M1.139 I.1-5 II.4-2S M1.140 I.1-5 II.4-1R M1.141 I.1-5 II.4-2R M1.142 I.1-5 II.5-1 M1.143 I.1-5 II.5-2 M1.144 I.1-5 II.5-3 M1.145 I.1-5 II.5-4 M1.146 I.1-5 II.5-5 M1.147 I.1-5 II.5-6 M1.148 I.1-5 II.5-7 M1.149 I.1-5 II.5-8 M1.150 I.1-5 II.5-9 M1.151 I.1-5 II.5-10 M1.152 I.1-5 II.6-1 M1.153 I.1-5 II.6-2 M1.154 I.1-5 II.6-3 M1.155 I.1-5 II.6-4 M1.156 I.1-6 II.1 M1.157 I.1-6 II.2-1 M1.158 I.1-6 II.2-2 M1.159 I.1-6 II.2-3 M1.160 I.1-6 II.2-4 M1.161 I.1-6 II.2-5 M1.162 I.1-6 II.2-6 M1.163 I.1-6 II.2-7 M1.164 I.1-6 II.2-8 M1.165 I.1-6 II.3-1 M1.166 I.1-6 II.3-2 M1.167 I.1-6 II.4-1 M1.168 I.1-6 II.4-2 M1.169 I.1-6 II.4-1S M1.170 I.1-6 II.4-2S M1.171 I.1-6 II.4-1R M1.172 I.1-6 II.4-2R M1.173 I.1-6 II.5-1 M1.174 I.1-6 II.5-2 M1.175 I.1-6 II.5-3 M1.176 I.1-6 II.5-4 M1.177 I.1-6 II.5-5 M1.178 I.1-6 II.5-6 M1.179 I.1-6 II.5-7 M1.180 I.1-6 II.5-8 M1.181 I.1-6 II.5-9 M1.182 I.1-6 II.5-10 M1.183 I.1-6 II.6-1 M1.184 I.1-6 II.6-2 M1.185 I.1-6 II.6-3 M1.186 I.1-6 II.6-4 M1.187 I.1-7 II.1 M1.188 I.1-7 II.2-1 M1.189 I.1-7 II.2-2 M1.190 I.1-7 II.2-3 M1.191 I.1-7 II.2-4 M1.192 I.1-7 II.2-5 M1.193 I.1-7 II.2-6 M1.194 I.1-7 II.2-7 M1.195 I.1-7 II.2-8 M1.196 I.1-7 II.3-1 M1.197 I.1-7 II.3-2 M1.198 I.1-7 II.4-1 M1.199 I.1-7 II.4-2 M1.200 I.1-7 II.4-1S M1.201 I.1-7 II.4-2S M1.202 I.1-7 II.4-1R M1.203 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I.1-19 II.5-10 M1.586 I.1-19 II.6-1 M1.587 I.1-19 II.6-2 M1.588 I.1-19 II.6-3 M1.589 I.1-19 II.6-4 M1.590 I.1-20 II.1 M1.591 I.1-20 II.2-1 M1.592 I.1-20 II.2-2 M1.593 I.1-20 II.2-3 M1.594 I.1-20 II.2-4 M1.595 I.1-20 II.2-5 M1.596 I.1-20 II.2-6 M1.597 I.1-20 II.2-7 M1.598 I.1-20 II.2-8 M1.599 I.1-20 II.3-1 M1.600 I.1-20 II.3-2 M1.601 I.1-20 II.4-1 M1.602 I.1-20 II.4-2 M1.603 I.1-20 II.4-1S M1.604 I.1-20 II.4-2S M1.605 I.1-20 II.4-1R M1.606 I.1-20 II.4-2R M1.607 I.1-20 II.5-1 M1.608 I.1-20 II.5-2 M1.609 I.1-20 II.5-3 M1.610 I.1-20 II.5-4 M1.611 I.1-20 II.5-5 M1.612 I.1-20 II.5-6 M1.613 I.1-20 II.5-7 M1.614 I.1-20 II.5-8 M1.615 I.1-20 II.5-9 M1.616 I.1-20 II.5-10 M1.617 I.1-20 II.6-1 M1.618 I.1-20 II.6-2 M1.619 I.1-20 II.6-3 M1.620 I.1-20 II.6-4 M1.621 I.1-21 II.1 M1.622 I.1-21 II.2-1 M1.623 I.1-21 II.2-2 M1.624 I.1-21 II.2-3 M1.625 I.1-21 II.2-4 M1.626 I.1-21 II.2-5 M1.627 I.1-21 II.2-6 M1.628 I.1-21 II.2-7 M1.629 I.1-21 II.2-8 M1.630 I.1-21 II.3-1 M1.631 I.1-21 II.3-2 M1.632 I.1-21 II.4-1 M1.633 I.1-21 II.4-2 M1.634 I.1-21 II.4-1S M1.635 I.1-21 II.4-2S M1.636 I.1-21 II.4-1R M1.637 I.1-21 II.4-2R M1.638 I.1-21 II.5-1 M1.639 I.1-21 II.5-2 M1.640 I.1-21 II.5-3 M1.641 I.1-21 II.5-4 M1.642 I.1-21 II.5-5 M1.643 I.1-21 II.5-6 M1.644 I.1-21 II.5-7 M1.645 I.1-21 II.5-8 M1.646 I.1-21 II.5-9 M1.647 I.1-21 II.5-10 M1.648 I.1-21 II.6-1 M1.649 I.1-21 II.6-2 M1.650 I.1-21 II.6-3 M1.651 I.1-21 II.6-4 M1.652 I.1-22 II.1 M1.653 I.1-22 II.2-1 M1.654 I.1-22 II.2-2 M1.655 I.1-22 II.2-3 M1.656 I.1-22 II.2-4 M1.657 I.1-22 II.2-5 M1.658 I.1-22 II.2-6 M1.659 I.1-22 II.2-7 M1.660 I.1-22 II.2-8 M1.661 I.1-22 II.3-1 M1.662 I.1-22 II.3-2 M1.663 I.1-22 II.4-1 M1.664 I.1-22 II.4-2 M1.665 I.1-22 II.4-1S M1.666 I.1-22 II.4-2S M1.667 I.1-22 II.4-1R M1.668 I.1-22 II.4-2R M1.669 I.1-22 II.5-1 M1.670 I.1-22 II.5-2 M1.671 I.1-22 II.5-3 M1.672 I.1-22 II.5-4 M1.673 I.1-22 II.5-5 M1.674 I.1-22 II.5-6 M1.675 I.1-22 II.5-7 M1.676 I.1-22 II.5-8 M1.677 I.1-22 II.5-9 M1.678 I.1-22 II.5-10 M1.679 I.1-22 II.6-1 M1.680 I.1-22 II.6-2 M1.681 I.1-22 II.6-3 M1.682 I.1-22 II.6-4 M1.683 I.1-23 II.1 M1.684 I.1-23 II.2-1 M1.685 I.1-23 II.2-2 M1.686 I.1-23 II.2-3 M1.687 I.1-23 II.2-4 M1.688 I.1-23 II.2-5 M1.689 I.1-23 II.2-6 M1.690 I.1-23 II.2-7 M1.691 I.1-23 II.2-8 M1.692 I.1-23 II.3-1 M1.693 I.1-23 II.3-2 M1.694 I.1-23 II.4-1 M1.695 I.1-23 II.4-2 M1.696 I.1-23 II.4-1S M1.697 I.1-23 II.4-2S M1.698 I.1-23 II.4-1R M1.699 I.1-23 II.4-2R M1.700 I.1-23 II.5-1 M1.701 I.1-23 II.5-2 M1.702 I.1-23 II.5-3 M1.703 I.1-23 II.5-4 M1.704 I.1-23 II.5-5 M1.705 I.1-23 II.5-6 M1.706 I.1-23 II.5-7 M1.707 I.1-23 II.5-8 M1.708 I.1-23 II.5-9 M1.709 I.1-23 II.5-10 M1.710 I.1-23 II.6-1 M1.711 I.1-23 II.6-2 M1.712 I.1-23 II.6-3 M1.713 I.1-23 II.6-4 M1.714 I.1-24 II.1 M1.715 I.1-24 II.2-1 M1.716 I.1-24 II.2-2 M1.717 I.1-24 II.2-3 M1.718 I.1-24 II.2-4 M1.719 I.1-24 II.2-5 M1.720 I.1-24 II.2-6 M1.721 I.1-24 II.2-7 M1.722 I.1-24 II.2-8 M1.723 I.1-24 II.3-1 M1.724 I.1-24 II.3-2 M1.725 I.1-24 II.4-1 M1.726 I.1-24 II.4-2 M1.727 I.1-24 II.4-1S M1.728 I.1-24 II.4-2S M1.729 I.1-24 II.4-1R M1.730 I.1-24 II.4-2R M1.731 I.1-24 II.5-1 M1.732 I.1-24 II.5-2 M1.733 I.1-24 II.5-3 M1.734 I.1-24 II.5-4 M1.735 I.1-24 II.5-5 M1.736 I.1-24 II.5-6 M1.737 I.1-24 II.5-7 M1.738 I.1-24 II.5-8 M1.739 I.1-24 II.5-9 M1.740 I.1-24 II.5-10 M1.741 I.1-24 II.6-1 M1.742 I.1-24 II.6-2 M1.743 I.1-24 II.6-3 M1.744 I.1-24 II.6-4

In one embodiment (E2), the invention relates to mixtures, wherein in the anthranilamide compound I

-   -   X is N;     -   R¹ is Br, Cl;     -   R² is CH₃, Cl, Br;     -   R³ is Cl, Br, C₁-C₄-haloalkyl;     -   R⁴ is NR⁷R⁸;     -   R⁷ and R⁸ are independently of one another hydrogen,         C₃-C₆-cycloalkyl, cyclopropylmethyl, cyclopropylethyl;     -   R⁹ is Cl and R¹⁰ is H.

In one embodiment, the invention relates to mixtures, wherein the anthranilamide compound I is the compound of formula I.2

Compound I.2 is known under the ISO name “cyclaniliprole” and is known from WO2005/077934.

In one embodiment, the invention relates to mixtures wherein the anthranilamide compound I is the compound I.2;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R

In one embodiment, the invention relates to mixtures as set out in Table M2.

TABLE M2 Mixture Compound I Compound II M2.1 I.2 II.1 M2.2 I.2 II.2-1 M2.3 I.2 II.2-2 M2.4 I.2 II.2-3 M2.5 I.2 II.2-4 M2.6 I.2 II.2-5 M2.7 I.2 II.2-6 M2.8 I.2 II.2-7 M2.9 I.2 II.2-8 M2.10 I.2 II.3-1 M2.11 I.2 II.3-2 M2.12 I.2 II.4-1 M2.13 I.2 II.4-2 M2.14 I.2 II.4-1S M2.15 I.2 II.4-2S M2.16 I.2 II.4-1R M2.17 I.2 II.4-2R M2.18 I.2 II.5-1 M2.19 I.2 II.5-2 M2.20 I.2 II.5-3 M2.21 I.2 II.5-4 M2.22 I.2 II.5-5 M2.23 I.2 II.5-6 M2.24 I.2 II.5-7 M2.25 I.2 II.5-8 M2.26 I.2 II.5-9 M2.27 I.2 II.5-10 M2.28 I.2 II.6-1 M2.29 I.2 II.6-2 M2.30 I.2 II.6-3 M2.31 I.2 II.6-4

In one embodiment, the invention relates to mixtures wherein the compound I is compound I.2 and the compound II is not the compound II.6-1 or II.6-2.

In one embodiment (E3), the invention relates to mixtures, wherein in the anthranilamide compound I

-   -   X is N;     -   R¹ is Cl or CN;     -   R² is CH₃, Cl, Br;     -   R³ a —CH₂-tetrazole radical;     -   R⁴ is NR⁷R⁸;     -   R⁷ and R⁸ are independently of one another hydrogen, or         C₁-C₆-alkyl;     -   R⁹ is Cl and R¹⁰ is H.

In one embodiment, the invention relates to mixtures, wherein the anthranilamide compound I is the compound of formula I.3

Compound I.3 is known under the ISO name “tetraniliprole” and is known from WO2007/144100 and WO2010/069502. It may be present also as a mixture of isomers, wherein the tetrazole moiety is either 2H-tetrazole or 1H-tetrazole, as described in WO2011/157664. Preferably the 2H-tetrazole is the main isomer.

In one embodiment, the invention relates to mixtures wherein the anthranilamide compound I is the compound I.3;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein the anthranilamide compound I is the compound I.3;

And wherein the compound II is the compound II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures as set out in Table M3.

TABLE M3 Mixture Compound I Compound II M3.1 I.3 II.1 M3.2 I.3 II.2-1 M3.3 I.3 II.2-2 M3.4 I.3 II.2-3 M3.5 I.3 II.2-4 M3.6 I.3 II.2-5 M3.7 I.3 II.2-6 M3.8 I.3 II.2-7 M3.9 I.3 II.2-8 M3.10 I.3 II.3-1 M3.11 I.3 II.3-2 M3.12 I.3 II.4-1 M3.13 I.3 II.4-2 M3.14 I.3 II.4-1S M3.15 I.3 II.4-2S M3.16 I.3 II.4-1R M3.17 I.3 II.4-2R M3.18 I.3 II.5-1 M3.19 I.3 II.5-2 M3.20 I.3 II.5-3 M3.21 I.3 II.5-4 M3.22 I.3 II.5-5 M3.23 I.3 II.5-6 M3.24 I.3 II.5-7 M3.25 I.3 II.5-8 M3.26 I.3 II.5-9 M3.27 I.3 II.5-10 M3.28 I.3 II.6-1 M3.29 I.3 II.6-2 M3.30 I.3 II.6-3 M3.31 I.3 II.6-4

In one embodiment (E4), the invention relates to mixtures, wherein in the anthranilamide compound I

-   -   X is N;     -   R¹ is Cl or CN;     -   R² is CH₃;     -   R³ a Cl, Br or C₁-C₄-haloalkyl;     -   R⁴ is NR⁷R⁸;     -   R⁷ and R⁸ are independently of one another hydrogen, or         C₁-C₆-alkyl;     -   R⁹ is Cl and R¹⁰ is H.

In one embodiment, the invention relates to mixtures, wherein the anthranilamide compound I is the compound of formula I.4

Compound I.4 is known under the ISO name “cyantraniliprole” and is known from WO2001/070671 and WO2004/067528. It is also commercially available.

In one embodiment, the invention relates to mixtures wherein the anthranilamide compound I is the compound I.4;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein, when the compound I is I.4 and the compound II is not the compound II.6-1 or II.6-2.

In one embodiment, the invention relates to mixtures, wherein the anthranilamide compound I is the compound of formula I.5

Compound I.5 is known under the ISO name “chlorantraniliprole” and is known from WO2001/070671 and WO2003/015519. It is also commercially available.

In one embodiment, the invention relates to mixtures wherein the anthranilamide compound I is the compound I.5;

and wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.

In one embodiment, the invention relates to mixtures wherein, when the compound I is I.5 and the compound II is not the compound II.6-1 or II.6-2.

In one embodiment, the invention relates to mixtures wherein, when the compound I is I.4 or I.5 and the compound II is not the compound II.6-1 or II.6-2.

Therefore the invention relates to mixtures as shown in Table M4.

TABLE M4 Mixture Compound I Compound II M4.1 I.4 II.1 M4.2 I.4 II.2-1 M4.3 I.4 II.2-2 M4.4 I.4 II.2-3 M4.5 I.4 II.2-4 M4.6 I.4 II.2-5 M4.7 I.4 II.2-6 M4.8 I.4 II.2-7 M4.9 I.4 II.2-8 M4.10 I.4 II.3-1 M4.11 I.4 II.3-2 M4.12 I.4 II.4-1 M4.13 I.4 II.4-2 M4.14 I.4 II.4-1S M4.15 I.4 II.4-2S M4.16 I.4 II.4-1R M4.17 I.4 II.4-2R M4.18 I.4 II.5-1 M4.19 I.4 II.5-2 M4.20 I.4 II.5-3 M4.21 I.4 II.5-4 M4.22 I.4 II.5-5 M4.23 I.4 II.5-6 M4.24 I.4 II.5-7 M4.25 I.4 II.5-8 M4.26 I.4 II.5-9 M4.27 I.4 II.5-10 M4.28 I.4 II.6-1 M4.29 I.4 II.6-2 M4.30 I.4 II.6-3 M4.31 I.4 II.6-4 M4.32 I.5 II.1 M4.33 I.5 II.2-1 M4.34 I.5 II.2-2 M4.35 I.5 II.2-3 M4.36 I.5 II.2-4 M4.37 I.5 II.2-5 M4.38 I.5 II.2-6 M4.39 I.5 II.2-7 M4.40 I.5 II.2-8 M4.41 I.5 II.3-1 M4.42 I.5 II.3-2 M4.43 I.5 II.4-1 M4.44 I.5 II.4-2 M4.45 I.5 II.4-1S M4.46 I.5 II.4-2S M4.47 I.5 II.4-1R M4.48 I.5 II.4-2R M4.49 I.5 II.5-1 M4.50 I.5 II.5-2 M4.51 I.5 II.5-3 M4.52 I.5 II.5-4 M4.53 I.5 II.5-5 M4.54 I.5 II.5-6 M4.55 I.5 II.5-7 M4.56 I.5 II.5-8 M4.57 I.5 II.5-9 M4.58 I.5 II.5-10 M4.59 I.5 II.6-1 M4.60 I.5 II.6-2 M4.61 I.5 II.6-3 M4.62 I.5 II.6-4

Additional Mixing Partners

The mixtures of the present invention may be combined and applied in agriculture in mixture with further active ingredients, for example with other pesticides, insecticides, nematicides, fungicides, herbicides, safeners, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators.

These mixtures are also embraced by the term “mixture(s) of the present invention” or “mixture(s) according to the invention”.

These additional ingredients may be used sequentially or in combination with the mixtures of the invention, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a mixture of this invention either before or after being treated with other active ingredients.

Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and the like. Preferred mixing partners are insecticides, nematicides and fungicides.

In one embodiment, the invention relates to ternary mixtures, comprising a compound I, a compound II and one further compound III, which is not identical to the compound I or II already present in the mixture.

In one embodiment, the invention relates to 4-way mixtures, comprising a compound I, a compound II and two further compounds III, which are not identical to the compound I or II already present in the mixture.

In one embodiment, the invention relates to 5-way mixtures, comprising a compound I, a compound II and three further compounds III, which are not identical to the compound I or II already present in the mixture.

Formulations

The invention also relates to agrochemical compositions comprising an auxiliary and at least one mixture of the present invention.

An agrochemical composition comprises a pesticidally effective amount of a mixture of the present invention. The term “pesticidally effective amount” is defined below.

The mixtures of the present invention can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo¬hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.)

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl-sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the mixtures of the present invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance.

The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising mixtures of the present invention, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising mixtures of the present invention, can be applied jointly (e.g. after tank mix) or consecutively.

Application Methods

The mixtures of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a mixture of the present invention.

The mixtures of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a mixture of the present invention.

The mixtures of the present invention are effective through both contact and ingestion. Furthermore, the mixtures of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.

The mixtures of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the mixtures of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above. The components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture “in situ” on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.

The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.

Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active mixture to the furrow, and closing the furrow.

Foliar application refers to the application of the pesticidally active mixture to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the mixtures of the present invention.

Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.phero-base.com.

As used herein, the term “contacting” includes both direct contact (applying the mixtures/compositions directly on the animal pest or plant—typically to the foliage, stem or roots of the plant) and indirect contact (applying the mixtures/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).

The term “animal pest” includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.

The term “crop” refers to both, growing and harvested crops.

The term “plant” includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize/sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, pumpkins, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g. carnation, petunias, geranium/pelargoniums, pansies and impatiens), shrubs, broad-leaved trees (e.g. poplar) or evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for animal feed or ornamental uses. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

The term “plant” is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof, in order to provide a new trait to a plant or to modify an already present trait.

Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.

Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.

Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.

Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.

Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicides: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.

Transgenic corn events comprising herbicide tolerance genes are for example, but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO-Ø1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.

Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTØH2, W62, W98, FG72 and CV127.

Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.

Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particular genes coding for protease inhibitors, like CpTI and pinII. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes. An example for such a transgene is dvsnf7.

Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.

Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701, MON87751 and DAS-81419.

Transgenic cotton events comprising genes for insecticidal proteins are for example, but not excluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.

Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.

Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.

Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-ØØ41Ø-5.

Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.

Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-gmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and WO2017/011288.

The use of compositions according to the invention on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors.

Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.

It has surprisingly been found that the pesticidal activity of the mixtures of the present invention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the mixtures of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the mixtures of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.

The term “plant propagation material” refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound or mixture either at or before planting or transplanting.

The term “seed” embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.

In general, “pesticidally effective amount” means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

In the case of soil treatment, in furrow application or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.

The mixtures of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermination with a mixture of the present invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.

The term “seed treatment” comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active mixture is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.

The present invention also comprises seeds coated with or containing the mixture(s) of the present invention. The term “coated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.

Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize/sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the mixture(s) of the present invention may also be used for the treatment of seeds from plants, which have been modified by mutagenesis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.

The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40% by weight.

In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

Especially preferred FS formulations of the mixtures of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20% by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5% by weight of a wetter and from 0.5 to 15% by weight of a dispersing agent, up to 20% by weight, e.g. from 5 to 20% of an anti-freeze agent, from 0 to 15% by weight, e.g. 1 to 15% by weight of a pigment and/or a dye, from 0 to 40% by weight, e.g. 1 to 40% by weight of a binder (sticker/adhesion agent), optionally up to 5% by weight, e.g. from 0.1 to 5% by weight of a thickener, optionally from 0.1 to 2% of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1% by weight and a filler/vehicle up to 100% by weight.

In the treatment of seed, the application rates of the mixtures of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.

The invention therefore also relates to seed comprising a mixture of the present invention, or an agriculturally useful salt thereof, as defined herein. The amount of the mixture of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.

The mixtures of the present invention may also be used for improving the health of a plant.

Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a mixture of the present invention.

As used herein “an effective and non-phytotoxic amount” means that the mixture is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.

The terms “plant” and “plant propagation material” are defined above.

“Plant health” is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves (“greening effect”), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).

The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by methods known to a skilled person.

The mixtures of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, mixtures of the present invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied). Furthermore, drenching and rodding methods can be used.

As used herein, the term “non-crop insect pest” refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g. http://www.phero-base.com), and are known to those skilled in the art.

For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of mixture(s) of the present invention.

Formulations of the mixtures of the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compounds or mixtures of the present invention, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate stabilizers, and, if required, propellants.

The oil spray formulations differ from the aerosol recipes in that no propellants are used.

For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

The mixtures of the present invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with mixtures of the present invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.

The mixtures of the present invention and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active mixture per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.

Pests

The mixtures of the present invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:

insects from the order of Lepidoptera, for example Achroia grisella, Acleris spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticarsia (=Thermesia) spp. such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca viridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticalis, L. cereralis; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp. such as M. americanum, M. californicum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mamestra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mocis spp. such as M. lapites, M. repanda; Mocis latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma saucia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. cosmoides, S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga tapetzella, Trichoplusia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubigalis, U. rubigalis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;

insects from the order of Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulenta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus brasiliensis, Faustinas cubae, Gibbium psyllioides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. such as L. bilineata, L melanopus; Leptinotarsa spp. such as L. decemlineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as M. alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon spp. such as P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp. such as X. pyrrhoderus; and, Zabrus spp. such as Z. tenebrioides;

insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactrocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipiens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphilus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fuscipes, G. morsitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Muscina stabulans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calcitrans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp;

insects from the order of Thysanoptera for example, Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;

insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Diaphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp. such as E. fabae, E. solana; Epidiaspis leperii, Eriosoma spp. such as E. lanigerum, E. pyricola; Erythroneura spp., Eurygaster spp. such as E. integriceps; Euscelis bilobatus, Euschistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, Icerya spp. such as I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corni, P. persicae; Pemphigus spp. such as P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp. such as P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri. P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. padi; Sagatodes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,

Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, Atta spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. floridanus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechina longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S. invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp;

Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chortoicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris septemfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. americana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus;

Pests from the Class Arachnida for example Acari, e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. microplus, Dermacentor spp. such as D. silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizoglyphus spp., Sarcoptes spp. such as S. scabiei; and Family Eriophyidae including Aceria spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pelekassi; Aculus spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldoni; Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki; Family Tenuipalpidae including Brevipalpus spp. such as B. phoenicis; Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. such as T. cinnabarinus, T. evansi, T. kanzawai, T. pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, Family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodex spp.; Family Trombicidea including Trombicula spp:, Family Macronyssidae including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici; Tyrophagus putrescentiae; Family Acaridae including Acarus siro; Family Araneida including Latrodectus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;

Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaimus spp. such as B. longicaudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Criconemoides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; Lance nematodes, Hoploaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as L. elongatus; Lesion nematodes, Pratylenchus spp. such as P. brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylenchorhynchus spp. such as T. claytoni, T. dubius; Citrus nematodes, Tylenchulus spp. such as T. semipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species;

Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longiceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as I. minor, I. snyder; Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis,

Insects from the order Blattaria for example Blatta spp. such as B. orientalis, B. lateralis; Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Periplaneta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Supella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis,

Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp., Ctenocephalides spp. such as C. felis, C. canis, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans, and Nosopsyllus fasciatus,

Insects from the order Thysanura for example Lepisma saccharina, Ctenolepisma urbana, and Thermobia domestica,

Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera coleoptrata;

Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp.,

Pests from the class Symphyla for example Scutigerella immaculata,

Insects from the order Dermaptera, for example Forficula auricularia,

Insects from the order Collembola, for example Onychiurus spp., such as Onychiurus armatus,

Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,

Insects from the order Phthiraptera, for example Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,

Examples of further pest species which may be controlled by the mixture(s) of the present invention include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

B. Biology

Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):

$E = {X + Y - \frac{XY}{100}}$

When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.

The analysis of synergism or antagonism between the mixtures or compositions was determined using Colby's equation.

BIOLOGICAL EXAMPLES

B.1 Green Peach Aphid (Myzus persicae)

For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at 23+1° C., 50+5% RH for 3 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table B1.

TABLE B1 Compounds ppm Average Control % I.1-1 0.8 0 II-4.1 2 0 I.1-1 + II-4.1 0.8 + 2 75* *synergistic control effect according to Colby's equation

B.2 Boll Weevil (Anthonomus grandis)

For evaluating control of boll weevil the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.

The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 20 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, microtiter plates were incubated at 23+1° C., 50+5% RH for 5 days. Egg and larval mortality was then visually assessed. For the mixture tested the results are listed in table B2.

TABLE B2 Compounds ppm Average Control % I.2 0.08 0 II-1 20 0 I.2 + II-1 0.08 + 20 50* *synergistic control effect according to Colby's equation

B.3. Yellow Fever Mosquito (Aedes aegypti)

For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of 96-well-microtiter plates containing 200 μl of tap water per well and 5-15 freshly hatched A. aegypti larvae.

The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, microtiter plates were incubated at 28±1° C., 80±5% RH for 2 days. Larval mortality was then visually assessed. For the mixture tested the results are listed in table B3.

TABLE B3 Compounds ppm Average Control % I.2 2  0 II-1 20 50 I.2 + II-1 2 + 20 100* *synergistic control effect according to Colby's equation 

What is claimed is:
 1. Pesticidal mixtures comprising as active compounds 1) at least one anthranilamide compound of formula (I):

wherein X is N, CF, CCl, CBr or Cl; R¹ is H, F, Cl, Br or CN, R² is CH₃, Cl, Br or F; R³ is F, Cl, Br, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or Q; R⁴ is N═S(O)_(k)R⁵R⁶ or NR⁷R⁸; R⁵, R⁶ are independently of one another hydrogen, C₁-C₄-alkyl, C₃-C₈-cycloalkyl, or R⁵ and R⁶ together represent a C₂-C₇-alkylene, C₂-C₇-alkenylene or C₆-C₉-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, k is 0 or 1; R⁷ and R⁸ are independently of one another hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, cyclopropylmethyl, cyclopropylethyl; R⁹, R¹⁰ are independently of one another H, F, Cl, Br; and Q is a —CH₂-tetrazole radical; or a stereoisomer, salt, crystalline form or N-oxide thereof; and 2) one or more pesticidally active compounds II selected from the group of 2.1. a compound of formula II.1

2.2. a compound of formula II.2 (II.2)

R^(II.2.1a) R^(II.2.1b) II.2-1 H CH₃ II.2-2 H Cl II.2-3 CH₃ Cl II.2-4 CH₃ CH₃ II.2-5 O—CH₂CH₃ CH₃ II.2-6 O—CH₃ CH₃ II.2-7 O—CH Cl II.2-8 O—CH₂CH₃ Cl

2.3. a compound of formula II.3-1 or II.3-2

2.4. a compound of formula II.4-1 or II-4.2

2.5. a compound of formula II.5

wherein the moiety —C(O)NHR^(II.5) in compounds II.5-1 to II.5-4 is connected to position 4 of the indazole moiety and the moiety —C(O)NHR^(II.5) in compounds II.5-5 to II.5-10 is connected to position 5 of the indazole moiety; 2.6. a compound of formula II.6

in a synergistically effective amount.
 2. Pesticidal mixtures according to claim 1, wherein a weight ratio of compound I and compound II is from 1000:1 to 1:1000.
 3. Pesticidal mixtures according to claim 1, wherein the compound II is the compound II.1, II.2-1, II.2-2, II.2-3, II.2-4, II.2-5, II.2-6, II.2-7, II.2-8, II.3-1, II.3-2 or II.4-1, II.4-2, II.4-1S, II.4-1R, II.4-2S, II.4-2R.
 4. Pesticidal mixtures according to claim 1, wherein in the compounds of formula I X is N; R¹ is Cl; R² is CH₃ or Cl; R³ is CF₃ or CHF₂; R⁴ is N═S(O)_(k)R⁵R⁶; R⁵, R⁶ are independently of one another hydrogen, C₁-C₄-alkyl, C₃-C₈-cycloalkyl, or R⁵ and R⁶ together represent a C₂-C₇-alkylene, C₂-C₇-alkenylene or C₆-C₉-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, k is 0 or 1; R⁹ is Cl and R¹⁰ is H.
 5. Pesticidal mixtures according to claim 4, wherein R⁴ is N═S(CH₃)₂, N═S(CH₂CH₃)₂, N═S(CH(CH₃)₂)₂.
 6. Pesticidal mixtures according to claim 1, wherein the compound of formula I is the compound of formula I.2:


7. Pesticidal mixtures according to claim 1, wherein the compound of formula I is the compound of formula I.3:


8. Pesticidal mixtures according to claim 1, wherein the compound of formula I is the compound of formula I.4:


9. Pesticidal mixtures according to claim 1, wherein the compound of formula I is the compound of formula I.5:


10. A method for controlling insects, acarids or nematodes comprising contacting an insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a mixture according to claim 1 in pesticidally effective amounts.
 11. A method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of a mixture according to claim
 1. 12. A method for protection of plant propagation material comprising contacting the plant propagation material with a mixture as defined in claim 1 in pesticidally effective amounts.
 13. Seed, comprising the mixture according to claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 14. A pesticidal composition, comprising a liquid or solid carrier and a mixture according to claim
 1. 